DE2255058B2 - Basic benzothiazole azo dyes, processes for their preparation and their use for dyeing and printing polymers and copolymers of acrylonitrile and dicyanoethylene, and acid-modified synthetic fibers - Google Patents

Description

The invention relates to basic dyes of the formula

^s > -N = N- b) fi \> R ₇ \ R ₅ N \ / in the N
I. I.
Rs (R R4

wherein

R ₂ and R ₈ halogen, alkyl, cyclohexyl, aralkyl, hydroxy, alkoxy, aryloxy, aralkoxy, nitro, alkoxycarbonyl, aryloxycarbonyl, aralkoxycarbonyl. Carboxy, cyano, thiocyan, acyl, acylamino, carbamoyl, N-alkyl-carbamoyl, Ν, Ν-dialkyl-carbamoyl, N-alkyl-N-aryl-carbamoyl, sulfamoyl, N-alkylsulfamoyl, Ν, Ν-dialkylsulfamoyl, alkylsulfonyl, Arylsulfonyl or trifluoromethyl mean, where the alkyl and alkoxy radicals have I to 6 carbon atoms. Aryl stands for phenyl, which can be substituted in the 2- or 4-position by chlorine or methyl, or stands for naphthyl, aralkyl for benzyl, phenylethyl, / I - phenyl - / I - hydroxy - ethyl or phenylpropyl (2,2) stands, and acyl is understood to mean the residue of an aliphatic, aromatic or heterocyclic carboxylic or sulfonic acid,

R., and R ₄ alkyl with 1 to 6 carbon atoms, alkenyl with 2 to 6 carbon atoms, cyclohexyl, benzyl, phenylethyl or phenylpropyl- (2,2),

R _{5 is} hydrogen, alkyl with 1 to 6 carbon atoms, cyclohexyl, benzyl, phenylethyl or phenylpropyl- (2.2),

R ,, hydrogen or alkyl with 1 to 6 carbon atoms, where R ₅ and R "can form a cyclohexane ring with one another,

R7 is hydrogen or alkyl having 1 to 6 carbon atoms, where R _e and R ₇ can form a cyclohexyl ring with one another.

ρ the numbers 0, I, 2,3 or 4,

/ j the numbers 0, I, 2 or 3 and

X "mean an anion, and

wherein the rings A and B can be fused with a benzene ring, the cyclic and acyclic groups of the radicals R ₃ to R ₇ can contain nonionic substituents and / or carboxyl groups, and the nonionic substituents are cationic dyes customary in the field below is more specified residues. This invention also provides mixtures of the dyes I, their preparation and use for dyeing and printing natural and synthetic materials.

The substituents present in the same ring can be identical or different.

Nonionic substituents in the context of the present invention are the following in dye chemistry Customary and under the reaction conditions in question not dissociated substituents such as Fluorine, chlorine, bromine; straight-chain or branched alkyl radicals with 1-6 carbon atoms; Aralkyl radicals; Alkenyl residues with 2-6 carbon atoms; Aryl radicals; Aikoxy remains. in particular Aikoxy radicals with 1-4 carbon atoms; Aralkoxy radicals; aryloxy radicals, alkyethio radicals, preferably alkylthio radicals with 1-3 carbon atoms; Aralkylthio radicals; Arylthio radicals; Nitro; Cyan; Alkoxycarbonyl, preferably those having an alkoxy radical with 1-4C atoms; the

jo formyl radical; Alkylcarbonyl radicals, especially those with an alkyl group with I-4C atoms; Arylcarbonyl-aralkylcarbonyl radicals; Alkoxycarbonyloxy radicals, preferably with an alkyl group with 1 to 4 carbon atoms; Alkylcarbonylamino radicals, preferably

j-, with an alkyl group with 1-4 C atoms, arylcarbonylamino radicals; Alkylsulfonylamino radicals, preferably with an alkyl group with 1-3 carbon atoms; Arylsulfonylamino groups, ureido, N-aryl or N-alkylureido, aryloxycarbonylami: io-, alkyloxy-

. (o carbonylamino-, carbamoyl-, N-alkyl-carbamoyl-, Ν, Ν-dialkylcarbamoyl, N-alkyl-N-aryl-carbamoyl-; Sulfamoyl-; N-alkylsulfamoyl-; N.N-dialkyl-sulfamoyl-; alkylsulfonyl-: alkenylsulfonyI- or aralkylsulfonyl radicals, where in said alkyl radicals

. (-, preferably I-4C atoms are present; arylsulfonyl, Carboxylic acid alkyl ester, carboxylic acid aryl ester, sulfonic acid alkyl ester and sulfonic acid aryl ester groups, where in each case straight-chain or branched alkyl radicals with 1-6 carbon atoms as alkyl groups, as

-, ο Aikoxy radicals those with 1-4 C atoms, as aryl radicals Phenyl and naphthyl and their derivatives such as 4-methylphenyl, 2-methylphenyl, 4-chlorophenyl, 2-chlorophenyl and 2-methyl-4-chlorophenyl and, as aralkyl radicals, phenylmethyl, phenylethyl, / f-phenyl-

π // - hydroxy-ethyl, phenylpropyl- (2,2) and, if appropriate, their derivatives substituted in the phenyl nucleus are exclusively suitable.

The organic and an-

M) organic anions into consideration.

Inorganic anions are, for example, fluoride, chloride, bromide and iodide, perchlorate, hydroxyl, Residues of S-containing acids such as hydrogen sulfate, sulfate, disulfate and aminosulfate; Residues of nitrogen

b5 oxygen acids, such as nitrate; Residues of oxyacids of phosphorus such as dihydrogen phosphate, hydrogen phosphate, phosphate and metaphosphate; Residues of carbonic acid, hydrogen carbonate and carbon

bonat; further anions of oxygen acids' ind Complex acids such as methosulfate, ethosulfate, hexafluorosilicate, Cyanate, thiocyanate, hexacyanoferrate (II), hexacyanoferrate (III), tri- and tetrachlorozincate, Tri- and tetrabromozincate, stannate, borate, divanadate, Tetravanadate, molybdate, tungstate, chromate, Bichromate and tetrafluoroborate, and anions of esters of boric acid, such as the glycerol ester of Boric acid and esters of phosphoric acid such as methyl phosphate.

Organic anions are, for example, anions of saturated or unsaturated aliphatic, cycloaliphatic, aromatic and heteroylic carboxylic acids and sulfonic acids, such as residues of formic acid, acetic acid, chloroacetic acid, cyanoacetic acid, hydroxyacetic acid, aminoacetic acid, methylaminoacetic acid, sulfamic acid, methyl-butyric acid, aminoethyl-butyric acid, i-Butyric acid, 2-methyl-butyric acid, 2-ethyl-butyric acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, 2-chloropropionic acid, 3-chloropropionic acid, 2-chlorobutyric acid, 2-hydroxypropic acid, 3-hydroxypropionic acid, thioglycolic acid, O-ethylglycolic acid malic acid, Dodecyltetraäthylenglykolätherpropionsäure, 3 - (nonyloxy) - propionic acid, 3 - (Isotridecyloxy) - propionic acid, 3 - (Isotridecyloxy) - diäthylenglykolätherpropionsäure, A therpropionsäure the alcohol mixture having from 6 to 10 carbon atoms, thioacetic acid, 6-BenzoyIamino-2-chlorocaproic, Nonylphenoltetraäthylengly kol ether propionic acid, nonylphenol diethylene glycol ether propionic acid, dodecyl tetraethylene glycol ether propionic acid, phenoxyacetic acid, nonylphenoxyacetic acid, n-valeric acid, i - valeric acid, 2,2,2-trimethyl acetic acid, n-caproic acid, stearic acid, stearic acid, oleic acid, n-caproic acid, n-caproic acid Lauric acid, a mixture of aliphatic carboxylic acids with 9 to 11 carbon atoms, a mixture of aliphatic carboxylic acids with 15 to 19 carbon atoms, the coconut fatty acid forerun, the undecanecarboxylic acid, n-tridecanecarboxylic acid and a coconut fatty acid mixture; of acrylic acid, methacrylic acid, crotonic acid, propargylic acid, oxalic acid, malonic acid, succleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid. Azelaic acid, the isomeric mixture of 2,2,4- and 2,4,4-trimethyladipic acid, sebacic acid, isosebacic acid (mixture of isomers), tartaric acid, citric acid, glyoxylic acid, dimethyl ether-a ^ '- dicarboxylic acid, methylene - bis - thioglycolic acid, dimethyl sulfide-λ , λ - dicarboxylic acid, 2,2 '- dithio - di - η - propionic acid fumaric acid, maleic acid, itaconic acid, ethylene bisiminoacetic acid, nitrilosulphonic acid, methanesulphonic acid, ethanesulphonic acid, chlorometliansulphonic acid, 2-chloroethanesulphonic acid, ie-methanesulphonic acid and 2-hydroxyethane Paraffin sulfonic acid, obtained by chlorosulfating paraffin oil !.

Suitable anions of cycloaliphatic carboxylic acids are ζ. B. the anions of cyclohexanecarboxylic acid, Cyclohexene-S-carboxylic acid and araliphatic anions Monocarboxylic acids are z. B. anions of phenylacetic acid, 4-methylphenylacetic acid and Mandelic acid.

Suitable anions of aromatic carboxylic acids are, for example, the anions of benzoic acid, ^{2-Methylbenzoes: i} acid, 3-methylbenzoic, 4-methylbenzoic acid, 4-tert-ButyIbenzoesäure, 2-bromobenzoic acid, 2-chlorobenzoic acid, 3 - Chlorbenzocsäu ^r e, 4-chlorobenzoic acid , 2,4-dichlorobenzoic acid, 2,5-dichlorobenzoic acid, 2-nitrobenzoic acid, 3-nitrobenzoic acid, 4 - nitrobenzoic acid, 2 - chloro - 4-nitrobenzoic acid, 6 - chloro - 3 - nitro - benzoic acid, 2,4 - dinitrobenzoic acid, 3 , 4 - dinitrobenzoic acid, 3,5 - dinitrobenzoic acid, 2 - hydroxybenzoic acid, 3 - hydroxybenzoic acid, 4 - hydroxybenzoic acid,

2 - mercaptobenzoic acid, 4 - nitro - 3 - methylbenzoic acid, 4-aminobenzoic acid, 5 - nitro - 2 - hydroxybenzoic acid, S-nitro ^ -hydroxybenzoic acid, 4-methoxybenzoic acid, 3 - nitro - 4 - methoxybenzoic acid, 4-chloro-3-hydroxybenzoic acid, 3-chloro-4-hydroxybenzoic acid, 5-chloro-2- hydroxy - 3 - methylbenzoic acid, 4-ethylmercaplo-2-chlorobenzoic acid, 2-hydroxy-3-methylbenzoic acid, 6-hydroxy-3-methylbenzoic acid, 2 - hydroxy - 4 - methylbenzoic acid, 6 - hydroxy - 2,4 - dimethylbenzoic acid, 6 - hydroxy

3 - tort. - butylbenzoic acid, phthalic acid, tetrachlorophthalic acid, 4 - hydroxyphiialic acid, 4 - methoxyphthalic acid, isophthalic acid, 4-chloroisophthalic acid, 5 - nitro - isophthalic acid, terephthalic acid, nitroterephthalic acid and diphenylcarboxylic acid - (3,4), ο - vanillic acid, 3 - sulfobenzoic acid, benzene tetracirboxylic acid - (1,2,4,5), naphthalenetetracarboxylic acid (1,4,5,8), bipheny! Carboxylic acid - (4), abietic acid, Phthalic acid mono - η - butyl ester, terephthalic acid monomethyl ester, 3 - hydroxy - 5,6,7,8 - tetrahydronaphthoic acid - (2), 2 - Hydroxynaphthoic acid (1) and anthraquinone carboxylic acid (2).

jo Suitable as anions of heteroyclic carboxylic acids are for example the anions of pyric acid. Dehydrogucic acid, indoly (3) acetic acid.

Suitable anions of aromatic sulfonic acids are

j5 z. B. the anions of benzene sulfonic acid, benzene disulfonic acid (l, 3), 4-chlorobenzenesulfonic acid, 3-nitrobenzenesulfonic acid, 6-chloro-3-nitrobenzenesulfonic acid, toluenesulfonic acid (4), toluenesulfonic acid (2), toluene (, i-sulfonic acid, 2-chlorotoluenesulfonic acid- (4), 2-hy-

,, j droxybenzenesulfonic acid, n-dodecylbenzenesulfonic acid. I, 2, .5,4-Tetrahydronaphthaiinsulphonic acid- (6), naphihalinsulphonic acid c - (I). Naphthalenedisulphonic acid- (1,4) or - (1,5), naphthalenetrisulphonic acid- (1,3,5), naphthol - (I) - sulfonic acid - (2), 5 - nitronaphthalenesulfonic acid- (2), 8-aminonaphthalenesulfonic acid - (1), stilbene disulfonic acid - (2,2 ') and biphenylsulfonic acid - (2). A suitable anion heicrocyclischer sulfonic acids is z. B. the anion of quinolinic acid (5).

Furthermore, the anions of Arylsulfin-.

-phosphonic and -phosphonous acids, such as benzenesulfinic and benzenephosphonic acid into consideration.

Colorless anions are preferred. For dyeing from an aqueous medium, such anions are preferred, the the Wasftflösüchkei! of the dye not too strong affect. Such anions are often also used for dyeing from organic solvents preferred which promote the solubility of the dye in organic solvents or at least not influence negatively.

bo The anion is generally given by the manufacturing process and the possible purification of the crude dye. In general, the dyes are as halides (especially lui chlorides or bromides) or as

b5 Methosulfates, ethosulfates, sulfates, benzene or toluene sulfonates or as acetates. The anions can act against other anions in a known manner be replaced.

Dyes of the general formula should be emphasized

Rio Rn

wherein R ₂ . R ,. R ₄ . R ₅ . R _n . η and X have the meaning given for formula 1 and

R., alkyl with I 4 carbon atoms.

R ₁ H is hydrogen or methyl and π

Rn is hydrogen or methyl, or R ₁₁ and R ₅ together are -CII, CII ₂ CH ₂ CH, -

Make kettc,
m the Paying. I. 2 or .1 means.

General dyes are of particular importance formula

R ₁₂ -O

, -N - N —Y

R.4

wherein R ₄ . R _1n . R _n . m. η and X have the meaning given for formula I or formula II and
R ₁₂ for methyl. "Xlhyl. Propyl or butyl.
R,., For methyl. Ethyl. Melhoxy. Älh'oxy. Chlorine.

Bromine. Fluorine. Trifluoromethyl. Phenoxy or benzyl oxy.
R ₁₄ for methyl. Ethyl. Propyl. Butyl. , i-chloroethyl.

, .- cyanoethyl. , .'-bromoethyl. ,, '- Ethoxyethyl.

, / - carboxyethyl. / i'-carbonamidoethyl. Allyl or

Benzyl.
R ₁₅ for methyl. Ethyl. Mcthoxy. Athoxy. Fluorine.

Chlorine. Bromine. Trifluoromethyl. Cyan. Thiocyanate.

Nitro. Carboxy. Aminocarbonyl. Aminosulfonyl.

Acetyl. Benzoyl. Phenoxy. Benzyloxv. Carboxylic acid-methyl-. -ethyl-. phenyl or benzene ester.

Methyl, ethyl or phenylsulfonyl.
R ₁ ,, for methyl. Phenyl. ; -Cvanpropyl or -Methoxycarbonyl-n-butyl.

From the formula III such dyes are to be emphasized in which R ₄ RiT,; - HydroxyäthyI.fi-ChloräthyI. η-butyl or benzyl. R ₁₂ for CH ₃ or C ₂ H ,. R ₁₄ and Ri "stand for CHj and m and η for 0.

Dyes of the general formula (III) are particularly valuable. in which R _{4 stands} for / ί-hydroxyethyl, and of these in turn those where R ,, for CHj or C ₂ H ₅ . Ri _h for CH ₃ and m and η for the number 0 stand.

Dyes of the general formula (III) are also of particular interest. in R ₄ for the rest

CH,

I "

R _r —C — OH

I.
R ₁₈

is where

R, - for hydrogen or methyl and

R ₁₈ for methyl. Ethyl, chloromethyl. Methoxymethyl. Ethoxymethyl. Propo.xymethyl. Butoxymethyl, allyloxymethyl. Phenoxy methyl or phenyl.

XA (Ru). N

H
R ₁ ,

(HD

Again, those with R _i2 CH _{1 are to be emphasized}

or C ₂ H ₅ . R ₁₁₁ = CH ,. R, - = H and m and "H = O.

Dyes of the formula I are by action

in of quaternizing agents of the general formula

R, -X
to azo dyes of the general formula

VN = N

(IV)

(V)

produced in a manner known per se. Here, X denotes a radical which can be _{split off as an anion, and R 2 to} R «./). / iA and B have them at Forme! ! given meaning.

Suitable quaternizing compounds are, for example, alkyl halides. Alkenyl halides. Aralkyl halides. Cycloalkyl halides. Dialkyl sulfates.

Allyl esters of aryl sulfonic acids and other esters of strong mineral acids and organic sulfonic acids, preferably of lower alcohols. The quaternizing agents can be further substituted , such as B. bromopropionic acid amide, bromopropionitrile. The action of these compounds can be used without or with the addition of a further solvent or in aqueous suspension at temperatures of 5-100 ⁰ C. preferably 15-90 ^c C., take place. This can involve the presence of a basic material such as magnesium oxide. Alkali carbonate, alkaline earth carbonate, potassium acetate, sodium hydrogen carbonate or mixtures of such basic materials may be indicated. Halobenzenes, for example, are suitable as solvents. Benzene hydrocarbons. Dialkyl ketones, haloalkanes (such as carbon tetrachloride, tetrachlorethylene, chloroform). Nitrobenzene. Dimethylformamide. Acetonitrile, glacial acetic acid, formic acid or alcohols.

cn,

R,

Rl:

(Vl

NH,

diazotized and then on indolines of the formula

(VII)

(VIII)

N-NH,

(IX)

The alkylation of azo dyes of the formula V to form basic dyes of the formula I is also successful by the action of acrylic acid or its derivatives, e.g. B. dos acrylamide, in the presence of a organic or inorganic acid such as acetic acid, formic acid, hydrochloric acid or mixtures thereof at temperatures between 50 and 100 "C. The Qu.virnierung can also by the action of Ethylene oxide or epoxy compound of the formula

10

occur, wherein R ₁₇ and R | _{H have} the meaning given above. This reaction takes place using rinns I oMinixmitlrk in counter « ¹ '! ^1. ! "'. CiiV.'i organic or inorganic acid which supplies the anion X, at temperatures of IO HX) C, preferably at 40-90" C. Suitable acids are e.g. B. sulfuric acid. Phosphoric acid, hydrochloric acid. Hydrogen bromide. Ben / .olsulfonic acid. Toluenesulfonic acid. Formic acid, acetic acid or propionic acid, whereby the liquid fatty acids can also be used as solvents. Dimethylformamide, for example, is also suitable as a solvent. Acetonitrile, dioxane. Tetrahydrofuran. Halobenzene. Benzene hydrocarbons. Nitrobenzene, dialkyl ketone, etc.

Compounds of the formula V are obtained in a manner known per se if 2-aminobenzothiazoles are used the formula

clutch.

R ₂ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , p, n, A and B have the meaning given for formula I.

Dyes of the formula I can also be prepared by adding hydrazones of the formula

2-amino-6-methnxy-ben / (hiazul, 2-Amino-6-ethoxy-benzothiazole, 2-Amino-6-methoxy-4-methyl-benzth! AzoI, 2-amino-5,6-dimethoxy-benzothiazole, 2-amino-4,6-dimeth () xy-benzthiazole, 2-amino-5-methyl-6-methoxy-benzthiazole, 2-amino-6 (- * - ethyl-capronyI-amino) -benzthiazole, 2-amino-benzothiazole, 2-amino-6-benzoylamino-benzothiazole, 2-Amino-6-acetylamino-benzthiazo !, 2-Amino-6-buty-oxy-benzothiazole, 2-Amino-6-propoxy-bcnzlhia / ol, Z-Aniino-o-methyl-benzothiazole. Suitable indolines of the formula VIII are, for example:

N-Met hyl-2-mct hy Iindoline, N-Ethyi-2-nicthylindoline. N-n-propyl-2-niet hy Iindoline.

N-n-Hiilvl-7-mi'lhvliniliiün

N-AIIy l-2-met hy Iindoline. N-benzyl-2-methyindoline, N-2'-chlorobenzyl-2-mcthyindoline. N-4'-chlorobenzy l-2-met hylindolin. N-4'-Met hy lbenzyl-2-mct hy Iindoline. N-Cyanmethyl-2-Met hylindolin, N - /> '- Cyanät hy l-2-Met hylindolin, N -,; - Hydroxyät hy l-2-met hy Iindolin. N- / i-ChloräthyI-2-Met hylindolin, Ν-, ϊ-bromate hy l-2-met hylindolin. N - // - Met hoxyät hy l-2-met hylindolin, N - // - Acctox ν ät hy l-2-met hylindolin, N -,; - Hydroxy-n-propyl-2-met hylindolin. N -, / - Hydroxy-n-buty l-2-met hylindolin. N -,; - Hydroxy-i-buty l-2-met hylindolin, N '/ Z-Hydroxy-j-methoxy-propy l-2-met hylindoline.

N- / i-Hydroxy -; - ethoxy-propyl-2-met hy Iindoline, N '/ i'-Hydroxy-v-propoxy-propy l-2-met hy Iindolin, N -,; - Hydroxy - / - butoxy-propy l-2-met hylindolin, N - ^ '- Hydroxy-z-allvloxy-propy l-2-met hy Iindolin, N '/ i'-Hydroxy - ^ - phenoxy-propy l-2-met hy Iindoline. N- / i-Hydroxy- / i-phenylethyl-2-met hy Iindoline, N-Met hyl-2,3,3-trimethyl-indoline, N-ethyl-2,3,3-trimethyl-indoline, N-butyl ^ J-trimethyl-indoline. N-AIIyl-2,3,3-trimelhyl-indoline, N-benzyl-2,3,3-trimelhyl-indoline, N-zi-hydroxyethyl ^ J-trimethylindoline, N- / i-chloroethyl-2,3,3-trimethylindoline, N- ^ i-acetoxyethyl-2,3,3-trimethylindoline. N-methyl-2 - / - cyanopropyl-3,3-dimethyl-indoline, N-methyl-2 - (-} '- methoxycarbonyl-n-buty I) -3,3-dimethyl-indoline. Mixture of:

N - ^ - Hydroxyethyl ^^^ - trimethyl-o-trifluoromethyl-indoline
and

60

oxidatively coupled to indolines of the formula VIII.

In formula IX, R ₂ , R3, ρ and A have the meaning given for formula I.

Suitable benzothiazoles of the formula VII are, for example:

^ yy
methylindoline.
Mixture of:

N - ^ - hydroxyethyl-2,3,3,6-tetramethylindoline and

N - /? - Hydroxyäthy! -2,3,3,4-tetramethylindoline, Nf-Hydroxyäthyl ^ J.SJ-tetramethylindoIin, 1,2,3,3,7-Pentamethylindoline, N- / ¥ -HydroxyäthyI-2,3,3-trimethyl-7-methoxyindoline,

N-methyl-hexahydrocarbazole,

N-ethyl-hexahydrocarbazole,
lhl

Mixture of:

1,2,3,3,6-pentamethylindoline
and

1,2,3,3,4-pentaniethylindoline,
N-zf-Hydroxyathyl ^ VM ^ -pentaniethylindolin, hl ^^ hlidli

Zyyyp
I-methyl-2-phenylindoline.
The new dyes of formula 1 are valuable dyes which can be used for dyeing and printing materials made of leather, tannic cotton, cellulose, synthetic super polyamides and super polyurethanes, as well as for dyeing lignin-containing fibers such as coconut, jute and sisal. They are also suitable for the production of writing fluids, stamp inks, ballpoint pen paste !! and can also be used in rubber printing.

Especially gecigiiei? .Uiii Füiiicii imί the basic Dyes of the formula I are flakes and fibers. Threads. Tapes, woven or knitted fabrics made from polyacrylonitrile or polyvinylidenecyanide or from copolymers of acrylonitrile with other vinyl compounds such as vinyl chloride, vinylidene chloride. Vinyl fluoride, vinyl acetate, vinyl pyridine, vinyl imidazole. Vinyl alcohol, Acrylic and methacrylic acid esters and amides, or flakes, fibers. Threads, ribbons. Woven or knitted fabrics from acid-modified aromatic polyesters and acid-modified polyamides. Sour modified aromatic polyesters are, for example, polycondensation products from sulfoterephthalic acid and ethylene glycol, d. H. Polyethylene glycol terephthalates containing sulfonic acid groups. like them in the Belgian U.S. Patent 449,179 and U.S. Patent 2,893,816.

The dyeing can be carried out from weakly acidic liquor, it being expedient to put it in the dyebath at 40-60 "C and then at boiling temperature colors. You can also dye under pressure at temperatures above 100 ° C. Furthermore spinning solutions can be added to the dyes for the production of polyacrylonitrile-containing fibers or also apply to the undrawn fiber.

The dyes of the formula I are superior in terms of their fastness properties to _{the products which carry hydrogen in the R 4 position.} The dyes can be used individually or in mixtures.

The dyes according to the invention and their mixture are good for coloring molded articles Polymers or copolymers of acrylonitrile, asymmetric dicyanethylene and acidic modified aromatic polyesters in chlorinated hydrocarbons suitable as a dye bath if they have the Solubility in chlorinated hydrocarbons promoting substituents such. B. the tertiary butyl group or carry the dodecyloxy group, or the anion X "is the anion of a monobasic organic acid with 4-30 carbon atoms.

The new dyes differ from known benzothiazolyl-diazacyanine dyes

ίο through the coupling component of the IndolinyI-5 type. Closest comparable dyes are coupling productsc of 2-aminobenzothiazoles and indoles. Carbazoles or aminobenzenes. These dyes are from DE-OS 21 29 271. US-PS 28 32 764.

π US-PS 31 36 751, US-PS 36 34 389. CH-PS 3 70 503 and .IA-PS 44-24 705 known. Opposite them stand out, as shown by numerous examples could be, the new dyes due to surprising advantages in the pH stability, in the reserve

2 '.) Vation of fibers that are not acid-modified, and in terms of lightfastness.

Example I.

In a mixture of 120 ml of glacial acetic acid and 60 ml 18 g of 1-amino-o-methoxybenzlhiazole are dissolved in water. Then 29 ml of 48% strength sulfuric acid are added and the corresponding 7 g of sodium nitrite are added dropwise at -5 ° C Amount of nitrosylsulfuric acid. After stirring for a further five hours at this temperature, I g Amidosulfonic acid is added and the resulting diazonium salt solution is then added dropwise to a mixture of 250 g of ice. 50 ml of water. 20 ml of 48% sulfuric acid and 17.7 g N-hydroxyethyl-2-methylindoline. One stirs one Hour at approx. -10 "C and then blunt by adding 20% sodium hydroxide solution drop by drop pH 4 from. The temperature is kept below 0 during this process.

The azo dye is filtered off with suction after the coupling has ended. washed with water and in vacuo dried. The black-violet powder obtained is stirred in 100 ml of chloroform and at the same time 18 g of dimethyl sulfate are added dropwise at the boiling point. Then stir for another 30 minutes with reflux cooling and then metered in 300 ml of boiling water. This distills Chloroform. 40 g of evaporated salt and 5 g of zinc chloride are added to the solution obtained at 50, and the mixture is cooled and the dyestuff which has crystallized out is filtered off with suction and dried in vacuo.

He has the formula

Cl "· ZnCl ₂

and dyes polyacrylonitrile fibers in blue hue ts Fr can also be represented by the

of good light and wet fastness. The dye quaternization instead of dimethyl sulfate with p-ToluoI-

is characterized by a very good resistance to boiling - sulfonic acid methyl ester or with methyl iodide

from. takes.

13th

Valuable dyes are also obtained if the following 2-aminobenzothiazoles are coupled with the indicated indolines in the manner described and 14

the azo dye freed from acid is methylated with dimethyl sulfate.

The coloration of the dyes on polyacrylonitrile results in the color shade listed with:

2-aminobenzothiazole

indoline Color on polyacrylonitrile

6-methoxy-6-ethoxy- 6-methoxy-6-ethoxy- 6-ethoxy-6-me'hoxy- 6-ethoxy-6-methoxy-6-ethoxy-6-methoxy-6-methoxy-6-methoxy-6-ethoxy-6-methoxy- 6-methoxy-6-methoxy- 6-methoxy-6-methoxy- o-methoxy-6-methoxy- 6-methoxy-6-methoxy-6-methoxy-6-methoxy-6-ethoxy-6-methoxy-6-methoxy-6-methoxy- 6-methoxy-6-methoxy- 6-methoxy-6-methoxy- 6-methoxy-6-methoxy- 6-methoxy-6-methoxy

6-methoxy

6-methoxy

6-methoxy

l-n-butyl-2-methylthylindoline

l - / (- Hydroxyethyl-2-methylindoline

1-benzyl-2-methylthylindoline

1-benzyl-2-methylindoline

i-n-butyl-2-methylthylindoline

l- / i-chlorethyl-2-methyl-thylindoline

! - / (- Chlorethyl ^ -mcthylindolin

! - // - Acctoxyethyl ^ -mcthylindoline

! - / i-Acctoxyethyl ^ -mcthylindulin

1-allyl-2-methylindoline

1-allyl-2-methylthylindoline

1 - / i-cyanoethyl-2-methylindoline

l - / <- cyanoethyl-2-methylthylindoline

1-cyano-methyl-2-methyl-thylindoline

l - / <- methoxyethyl-2-methylindoline

l- / f-hydroxy-n-propyl-2-methylthylindoline

l- / i-Hydroxy-n-butyl-2-methylthylindoline

! - / i-Hydroxy-zi-phenylethyl ^ -mcIhylindoline

1-n-propyl-2-methylthylindoline

l - / <- Bromoethyl-2-methylethylindoline

l- / ί-hydroxy -; - allyloxy-n-propyl-2-methylthylindoline

l- / i-hydroxy -; - methoxy-n-propyl-2-methylthylindoline

l- / i-Hydroxy --- ethoxy-n-propyl-2-mclhylindo! in

l-Zi-Hydroxy-j-chloro-n-propyl - ^ - mcthylindolin

l - / <- Hydroxy -; - Chlorine-n-propyl-2-methylthylindoline

1- (4'-Chlorobenzyl) -2-methylindoline

1- (2'-ChlorbenzyI) -2-methylindoline

1- (4'-methylbenzyl) -2-methylethylindoline

1-isopropyl-2-methylindoline

I 2,3,3-tetramethylindoline

1-Ethyl ^ JJ-trimcthylindoIin

l-n-butyl-2,3.3-trimethylindoline

1-allyl-2,3,3-trimethylindoline

l - / * - hydroxyethyl-2,3,3-trimethylindoline

l - / <- chloroethy1-2,3,3-trinriethylindoline

Mixture of

1,2,3,3,6-pentamethylindoline

and

1,2,3,3,4-pentamethylindoline

Mixture of

l - / <- hydroxyethyl-2,3,3,6-tetramethylindoline

and

l- / i-hydroxyethyl-2,3,3,4-tetramethylindoline

Mixture of

! - / i-Hydroxyethyl-l ^^ - trimothyl- ^ trifluoromethylindoline

and

l- / i-hydroxyethyl-2 _> 3,3-trimethyl-6-trifluoromethylindoline

blue

blue

blue

blue

blue

blue

blue

blue

blue

blue

blue

blue

blue

rolling. blue

blue

blue

blue

blue

blue

blue

blue

blue

blue

blue

blue

blue

blue

blue

blue

blue

blue

blue

blue

blue

blue

blue

blue

blue

Blue blue

continuation

2-aminobenzothiazole indoline < 6-methoxy l 6-methoxy- I ^ 3,3,6,7-hexamethylene indoline Hue on 6-methoxy-1 - / (- Hydroxyethyl ^ .S.oJ-pentamelhylindolin Polyaaylnitri 6-melhoxy- 6-methoxy 1,3,3-trimethyl-2 -} '- cyanopropylindoline blue 6-methoxy 6-methoxy ^^ Trimethyl ^ -iy-methoxycarbonyl-n-butylI-indoline blue 6-methoxy 6-ethoxy , 2,3,3-tetramethyl-7-melhoxyindoline blue 6-melhoxy- 6-methoxy ^ S ^ -Tetramethyl ^ -chloro-indoline blue 6-methoxy 6-methoxy ^, 3,3,7-pentamethylindoline blue 6-mithoxy- 6-Mciiioxy- somehow blue 6-methoxy 6-methoxy AS ^ -Tetramethyl-o-chloroindoline blue 6-methoxy md 6-methoxy -Cvanmethyl ^ SJ-trimethylindoline blue 6-methoxy- "" 1-methyl-hexahydrocarbazole 6-benzoylamino ^ -Ethyl-hexahydrocarbazole rust. blue 6-benzoylamino -Methyl-2-phenylindoline blue 6-acetylamino -Methyl-2-phenylindoline Navy blue 6- (x-ethyl-capronylV - / (- Hydroxyethyl-2-phenylindoline blue amino - / {- chloroethyl-2-phenylindoline blue 6-metho>; y-4-methyl- - / i-Aceloxyethyl-2-phenylindoline blue o-methoxy ^ methyl- -Ethyl-2-phenylindoline blue 5,6-dimethoxy -Methyl-2-p-methylphenylindoline blue 4,6-dimethoxy -Methyl-2-p-methoxyphenylindoliti blue 6-metho); y- - / »'- Methoxyethyl-2-phenylindoline blue Mix of -Benzyl-2-methylindoline blue S-methyl-e-methoxy- - / (- Hydroxyethyl-2-methylindoline blue and -Benzyl-2-methylindoline blue 7-methyl-6-methoxy - / (- Hydroxyethyl-2-methylthylindoline blue 6-propoxy blue 6-butoxy - /> - Hydroxyethyl-2-methylthylindoline blue 2-aminobenzothiazole -Ben;: yl-2-methylindoline 6-benzyloxy - / (- Hydroxyethyl-2-methylindoline blue 6-parts-butyl- - / (- Hydroxy-ethyl-2-rnelhylindoliii blue 6-methyl - / (- Hydroxy-j-phenoxy-n-propyl · 2-ticthylindoline blue 6-benzyl blue 4,6,7-trimethyl blue 4,6-dimethyl 6-ethyl - / (- Hydroxyethyl-2-methylindoline 6-mclhoxy- - / (- Hydroxyethyl-2-methylindoline 6-ethoxy - / (- Hydroxyethyl-2-methylthylindoline blue 6-methyl - / {- Hydroxyethyl-2-methylthylindoline blue 6-melhoxy- - / i-HydrDxyäthyl-2-mcthylindolin blue 6-methoxy - / (- Hydroxyethyl-2-methylindoline rotst. blue 6-methoxy - / (- Hydroxyethyl-2-methylthylindoline blue - / (- Hydroxyethyl-2-methylthylindoline blue - / {- Hydroxyethyl-2-methylthylindoline blue - // - Hydroxyethyl-2-methylindoline blue - / i-Hydroxyethyl-2-methylindoline blue -Cyclohexyl ^ -methylindoline blue -Cyclohexyl ^ -methylindoline blue -Benzyl-2-methylindoline blue - / {- (Phenylamino-carbonyloxy) -ethyl-2-methylindoline blue ^ - / (- ((D-Hydroxyethyloxy) -ethyl-2-methylindoline blue ^! - / (- (i. <- Chloräthyloxy) -äthyl-2-mcthylindolin blue blue blue
90

Example 2

If you proceed as in Example I and then instead of dimethyl sulfate the equivalent amount of diethyl sulfate

begins, whereby it is expedient to limit the duration of the Extending the alkylation to 6 hours gives the dye of the formula:

H ₃ CO

NC ₂ H ₄ OH

Cl '· ZnCl ₂

It is characterized by very good resistance to boiling and colors polyacrylonitrile with blue Hue. Similar good results are obtained if one looks at the preparation in the table too Example! ! mentioned dyes with diethyl sulfate instead of dimethyl sulfate works.

Example 3

20 g <5 of the azo dyes described in Example I not reacted with dimethyl sulfate are mixed with 30 ml of acetonitrile and 30 ml of n-butyl bromide are mixed together, mixed with 1 g of magnesium oxide and heated to 80-85 ° C for 12 hours. Then the solvents distilled off in the vacuum of the water jet pump. The distillation residue is dissolved in hot water and clarified with 3 g Α charcoal. Then it is precipitated with evaporated salt, and the dye is separated off from the solution and dries in a vacuum. The reaction product has

25 the formula

H ₃ CO

CH,

C ₂ H ₄ OH he

It dyes polyacrylonitrile in a blue shade. Example 4

A diazonium salt solution prepared as described in Example I from 18 g of 2-amino-6-methoxybenzthiazole is added dropwise at -10 "within for 1 hour, 22.3 g of N-benzyl-2-methylindoline are stirred 30 minutes and then add 300 g of ice.

The acidic salt of the azo dye crystallizes in the process. It is filtered with suction after 5slündigcm stirring below 0 ^r 'C, washed with water and again stirred with 300 ml of water. Then one drips baking soda soak in until a pH value of 8 remains, squeezes off, washed with water and dried in vacuo.

The dried product is at 50 ° in 50 ml Glacial acetic acid stirred. Ethylene oxide is then introduced

and slowly increases the temperature to 80 °.

4> As soon as the thin-layer chromatogram is good too pursuit of qualification has ended, the solution is stirred into 250 ml of 20% strength evaporated salt solution and stirred a few minutes and then presses off the crystallized dye. It is dried in a vacuum

■ so and will crack in quantitative yield. The product has the formula:

CH ₃

Cl "

It colors polyacrylonitrile in a blue shade and is characterized by very good boiling properties.

19th Example 5 ^H3CO YY ^S > N = NA 1 20th ⁺ cr , so the implements and then with the mentioned ndolin Quaternized with Hue on If you work as indicated in Example 4 and give instead of Athylenoxk Epoxies! quaternized. The precipitation of the examples on polyacrylonitrile gives the color shades indicated with. Polyacrylonitrile analogous work-up the dye of the formula L N
CH, j 12.5 g of 1 ^ -butylene oxide 2-aminobenzothiazole -Mcthy 1-2-pheny I indole in Ethylene oxide blue 22 55 058 CHOH ι ²
CH, Λ} - / i-Hydroxyäthyi-2-methylindoline Ethylene oxide blue CH ₃ ^ / 6-methoxy -n-butyl-2-methylindoline Ethylene oxide blue likewise stains blue with good fastness properties. CH ₃ 6-methoxy -Penzyl-2-methylindoline Ethylene oxide blue 6-methoxy -p-chlorobenzyl ^ -niethylindoline Ethylene oxide blue 6-ethoxy -o-Chiorbenryi ^ -methylindoline Ethylene oxide blue the polyacrylonitrile Valuable dyes are also obtained if one works as in Examples 4 and 5, while those in the following 6-methoxy -p-methylbenzyl-2-i-ethylindoline Ethylene oxide blue Table listed 2-aminobenzthiazoIe and indolines with each other P o-mcihöXy- - / i-Hydroxyethyl-2-phenyIindoline Ethylene oxide blue a 6-methoxy- , 2-dimethylindoline Ethylene oxide blue > § 6-methoxy- -Allyl-2-methylindoline Ethylene oxide blue I 6-methoxy- - / <- chloroethyl-2-methylindoline Ethylene oxide blue 1 6-methoxy - / y-Hydroxy-n-butyl-2-methylindoline Ethylene oxide blue f 6-methoxy - / i-Hydroxy-y-chloro-n-propyl-2-methylindoline Ethylene oxide blue ! $ 6-methoxy- - Benzyl-2-methy I indole i η Propylene oxide blue I 6-methoxy- - / i-Hydroxyethyl-2-methylindoline Propylene oxide blue i 6-methoxy- -Ethyl ^^ - trimethylindoline Ethylene oxide blue I 6-methoxy- - / <- Hydroxyethyl-2,3,3-trimethylindoline Ethylene oxide blue I 6-methoxy- -Benzyl-2-methylindoline Ethylene oxide blue b 6-methoxy- - / i-Hydroxyethyl-2-methylindoline 1,2-butylene oxide blue ; | 6-methyl- - / f-Hydroxyethyl-2-methylindoline y-phenoxypropylene oxide blue I 6-methyl -Benzyl-2-methylindoline γ- phenoxypropylene oxide blue fej 6-methoxy- - // - Hydroxyethyl-2-methylindoline γ-allyloxypropylene oxide blue I 6-methoxy- -Benzyl-2-methylindoline ) -A! Lyloxypropylene oxide blue D 6-methoxy - / <- Hydroxyethyl-2-methylindoline 1,2-butylene oxide blue ■■ 6-methoxy- - / i-Hydroxyethyl-2-methylindoline y-methoxypropylene oxide blue I 6-methoxy- -Benzyl-2-methylindoline j'-methoxypropylene oxide blue I 6-methoxy- - // - Hydroxyethyl-2-methylindoline } Ethoxypropylene oxide blue w 6-methoxy -Benzyl-2-methylindoline ) '- ethoxypropylene oxide blue s | 6-methoxy-
I 6-methoxy- - // - Hydroxyethyl-2-methylindoline y-butoxypropylene oxide blue 6-methoxy -Benzyl-2-methylindoline y-butoxypropylene oxide blue 6-methoxy -Cyanäthyl ^ -melhylindolin 1,2-butylene oxide blue 6-methoxy Cyanoethyl-2-methylindoline Ethyl oxide blue 6-methoxy Cyanoethyl-2-methylindoline Propylene oxide blue 6-methoxy - / i-Acetoxyethyl-2-methylindoline Propylene oxide blue o-methoxy

continuation

2-aminobenzthinene] ndolin Quaternized with Hue on Polyacrylonitrile 6-methoxy - / iAcetoxyethyl-2-methylindoline 1,2-butylene oxide blue 6-metho. \ Y- -Butyl-2-methylindoline 1,2-butylene oxide blue 6-melhoxy- -ButyI-2-methylindoline Propylene oxide Biau 6-methoxy - / i-Hydroxyethyl-2-methylindoline Epichlorohydrin blue 6-methoxy -Benzyl-2-methylindoline Epichlorohydrin Biau 6-methoxy - / i- (Phenylaniino-carbonyloxy) -ethyl- Ethylene oxide blue ! -methylindoline Example 6 Example 8

A polyacrylonitrile fabric is printed with a printing paste, which is produced in the following manner was: 30 parts by weight of that described in Example i Dye, 50 pounds by weight of thiodiethylene glycol, 30 parts by weight of cyclohexanol and 30 parts by weight of 30% acetic acid are mixed with 330 parts by weight Poured hot water over the resulting solution to 500 parts by weight of crystal rubber (Gum arabic as a thickener). Finally, 30 parts by weight of zinc nitral solution are added added. The pressure obtained is dried, steamed for 30 minutes and then rinsed. Man receives a blue print with very good fastness properties.

Example 7

Acid-modified Polyglykolterephthalatfasern are grown at 20 ⁰ C in a liquor ratio 1: 40 is introduced into an aqueous bath containing, per liter of 3 to 10 g of sodium sulfate, 0.1 to 1 gOIey polygIykoläther (50 mol Äthyle.ioxid), 0- 15 g and 0 Dimethylbenzyldodecylammoniumchlorid Contains 15 g of the dye described in the table for Example 1 at the first position and was adjusted to pH 4 to 5 with acetic acid. It is heated to 100 ^° C. within 30 minutes and the bath is kept at this temperature for 60 minutes. The fibers are then rinsed and dried. A blue dyeing with good fastness properties is obtained.

Pclyacrylonitrilfaschen are at 40 ° C in the liquor ratio 1: 40 placed in a water bath containing 0.75 g of 30% strength acetic acid and 0.38 g of sodium acetate per liter and 0.15 g of the dye described in Example I. It is heated within 20 to 30 minutes to the boil and keep the bath at this temperature for 30 to 6 ° minutes. After rinsing and drying gives a blue dyeing with very good fastness properties.

Example 9

A stock solution is prepared from 15 parts by weight of the dye mentioned in Example 1, 15 parts by weight of polyacrylonitrile and 70 parts by weight of dimethylformamide, which is added to a conventional spinning solution of polyacrylonitrile and spun in a known manner. A blue Fär- Vy environment of very good Echtheitseigenschaflen.

Example 10

Acid modified synthetic polyamide fibers are at 40 ⁰ C in a liquor ratio 1:40 in a

4 · aqueous bath introduced containing 10 g of sodium acetate per liter, 1 to 5 g of oleyl polyglycol ether (50 mol of ethylene oxide) and 0.3 g of that described in Bcispici 1 Contains dye and with acetic acid to pH 4-5 was discontinued. The mixture is heated to 98 ° C. in the course of 30 minutes and the bath is kept at this temperature. The fibers are then rinsed and dried. A blue color is obtained.

Claims (1)

Patent claims:
1. Dyes of the general formula 22 55 Q58 wherein R, and R ₈ halogen, alkyl, cyclohexyl, aralkyl, hydroxy, alkoxy, aryloxy, aralkoxy, nitro, alkoxycarbonyl, aryloxycarbonyl, aralkoxycarbonyl, carboxy, cyano, j thiocyan, acyl, acylamino, carbamoyl, N-alkyl-carbamoyl, N, N-dialkylcarbamoyl, N-alkyl-N-aryl-carbamoyl, sulfamoyl, N-alkyl-sulfamoyl, N, N-dialkyl-sulfamoyl, alkylsulfonyl, arylsulfonyl or trifluoromethyl, arylsulfonyl or trifluoromethyl! mean, where the alkyl and alkoxy radicals I have to 6 carbon atoms, aryl stands for phenyl, which can be substituted in the 2- or 4-position by chlorine or methyl, or stands for naphthyl, aralkyl for benzyl, phenylethyl , _w / f-phenyl- ^ hydroxy-ethyl or phenylpropyl- (2.2), and acyl means the residue of an aliphatic, aromatic or heterocyclic carboxylic or sulfonic acid, R ₃ and R ₄ alkyl with 1 to 6 carbon atoms, alkenyl with 2 to 6 carbon atoms, cyclohexyl, benzyl, phenylethyl or phenyIpropyl- (2 ^), ίο R ₅ hydrogen, alkyl with 1 to 6 carbon atoms, cyclohexyl, benzyl, phenylethyl or phenylpropyl- (2.2),
R _{6 is} hydrogen or alkyl with 1 to 6 Koh lenstoffatomen, where R ₅ and R ,, can form a cyclohexane ring with one another, R ₇ hydrogen or alkyl with I Ms 6 Koh lenstoffatomen, where Rh urxu R ₇ can form a cyclohexyl ring with one another, ρ the numbers 0,!, 2, 3 or 4, ; i the numbers 0,1,2 or 3 and X "mean an anion, and wherein the rings A and B can be fused with a benzene ring, the cyclic and acyclic groups of the radicals R ₃ to R ₇ can contain further nonionic substituents and / or carboxyl groups specified in more detail in the description.
2. Dyes of the general formula R., R ₉ alkyl with 1-4 carbon atoms, R _{10 is} hydrogen or methyl and R ₁₁ denotes hydrogen or methyl, or R _M and R ₅ together represent a —CH ₂ —CH ₂ - Form CH ₂ -CH ₂ -KeHe,
m means the numbers 0, I, 2 or 3, and the other symbols have the meaning of claim I. 3. Process for the preparation of dyes of claim I, characterized in that mail dyes of the general formula my formula
4-, R ₃ -X wherein R _{3 has} the meaning of claim I, and X means a residue that can be split off as X, implements. 4. The method according to claim 3, characterized in that that the quaternization with ethylene oxide in the presence of an acid which supplies the anion X "is carried out. v> 5. The method according to claim 3, characterized in that that you can quaternize with epoxides of the general formula CH ₂ wherein the symbols have the meaning of claim I, with quaternizing agents of the allgeworin Rn is hydrogen or methyl and R ₁₈ denotes methyl, ethyl, chloromethyl, methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, allyloxymethyl], phenoxymethyl or phenyl, in the presence of an acid which gives the anion X ~, carries out. 6. Process for dyeing and printing polymers and copolymers of acrylonitrile or of dicyanoethylene, of acid-modified polyesters and acid-modified superpolyamides, of leather, paper, tanned cotton, writing fluids, printing pastes and lignin-containing Fibers, characterized in that dyes of claims 1 and 2 are used.